Unexpected Alternated Radical Copolymerization of Vinylidene Cyanide with a Fluorinated Vinyl Ether for Superhydrophobic and Highly Oleophobic Films

Abstract

The synthesis and the characterization of original copolymers based on vinylidene cyanide (VCN) and 1H,1H,2H,2H-perfluorodecyl vinyl ether (FAVE8) are presented. While VCN is known to be very reactive in radical homopolymerization in contrast to the vinyl ether which does not homopolymerize, the radical copolymerization of VCN with FAVE8 unexpectedly led to alternating poly(VCN-alt-FAVE8) copolymers. Seven radical copolymerization reactions were investigated with [VCN] 0 /[FAVE8] 0 percent molar ratios ranging between 15/85 and 80/20. The copolymer compositions of these copolymers were assessed by elemental analyses and showed 32 mol. % (in one case only) to 56 mol. % of VCN (ca. 50 mol % in most cases). From the monomer -polymer copolymerization curve, the Fineman-Ross and Kelen-Tüdos laws enabled to assess the reactivity ratios (r VCN = r 12 = 0.08 ± 0.01; r FAVE8 = r 21 = 0.07 ± 0.01 at 75 °C) while the Revised Patterns Scheme led to r 12 = 2.7 x 10 -3 and r 21 = 4.0 x 10 -6 suggesting an alternating tendency of that radical copolymerization. Thermogravimetric analysis of these copolymers showed exceptional thermal stability, the

Thermal degradation behaviour of a nearly alternating copolymer of vinylidene cyanide with 2,2,2-trifluoroethyl methacrylate

“…According to the differential method proposed by Friedman, by taking the logarithmic form of equation (6) lnðbda=dTÞ ¼ lnðda=dtÞ ¼ ln½k 0 ,f ðaÞ À E=RT (9) one should obtain linear isoconversion plots of ln (da/dt) against 1/T from the TG data recorded at different heating rates, the different conversions resulting in parallel interpolations. The activation energy can thus be evaluated from the slope of the linear fit.…”

“…The activation energy can thus be evaluated from the slope of the linear fit. The working relationship for the integral FWO method is also obtained from equation (6). After rearrangement, separation of the variables and integration, the logarithmic form is considered: logb ¼ logðk 0 E=gðaÞRÞ þ logpðxÞ (10) in which x ¼ E/RT and pðxÞ ¼ R N…”

“…Within this class of polymers, those in which the presence of fluorine atoms or side chain fluoroalkyl moieties is associated with that of other highly polar main chain substituents, such as the nitrile group, are of interest for the development of advanced materials for electrical [5] and coating [6] applications. Due to their strong electron withdrawing effect, these substituents can significantly affect the reactivity of the respective monomers, allowing to obtain more or less regularly alternating copolymer structures when copolymerized with more nucleophilic monomers.…”

Structural analysis and surface wettability of a novel alternated vinylidene cyanide with fluorinated vinyl ether copolymer

“…The cationic polymerization of a fluorinated vinyl ether, such as 1H,1H,2H,2H-perfluorooctyl vinyl ether, was reported by Vandooren et al 16,17 This reaction was initiated using a HI/ZnI 2 system, which formed living poly(ether)s that bore fluoroalkyl side groups. A few copolymers based on perfluorooctyl ethyl vinyl ether (FAVE8) and ethylene, 27 tert-butyl 2-trifluoromethyl acrylate, 28 vinylidene cyanide (VCN) 29 or chlorotrifluoroethylene 30 have been reported. These last two copolymers are alternated with the last one showing remarkable thermal and superhydrophobic properties.…”

Micro–nano hierarchically structured nylon 6,6 surfaces with unique wettability

“…Immense attention has been given to surfaces with unique wetting phenomena in both the industry and scientific communities lately [1][2][3][4][5][6][7][8][9][10][11]. Water contact angle (CA) is used to characterize the wetting behavior of a water droplet on the solid substrate.…”